WO2020138802A1 - Composition de résine thermoplastique et article moulé produit à partir de celle-ci - Google Patents

Composition de résine thermoplastique et article moulé produit à partir de celle-ci Download PDF

Info

Publication number
WO2020138802A1
WO2020138802A1 PCT/KR2019/017783 KR2019017783W WO2020138802A1 WO 2020138802 A1 WO2020138802 A1 WO 2020138802A1 KR 2019017783 W KR2019017783 W KR 2019017783W WO 2020138802 A1 WO2020138802 A1 WO 2020138802A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermoplastic resin
resin composition
weight
formula
parts
Prior art date
Application number
PCT/KR2019/017783
Other languages
English (en)
Korean (ko)
Inventor
이진성
오현지
정현택
허준혁
권영철
Original Assignee
롯데케미칼 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 롯데케미칼 주식회사 filed Critical 롯데케미칼 주식회사
Priority to US17/284,858 priority Critical patent/US20210388140A1/en
Priority to EP19901687.4A priority patent/EP3904455A4/fr
Priority to CN201980075671.5A priority patent/CN113056521A/zh
Publication of WO2020138802A1 publication Critical patent/WO2020138802A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C08K5/5373—Esters of phosphonic acids containing heterocyclic rings not representing cyclic esters of phosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer

Definitions

  • the present invention relates to a thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent hydrolysis resistance, flame retardancy, impact resistance, and balance of physical properties, and a molded article formed therefrom.
  • thermoplastic resin composition including polycarbonate resin, rubber-modified aromatic vinyl-based copolymer resin, and flame retardant is excellent in impact resistance, flame retardancy, and workability, so that the housing of electrical/electronic products that generate a lot of heat and other office equipment / Useful as exterior materials.
  • thermoplastic resin composition comprising a polycarbonate resin and a rubber-modified aromatic vinyl-based copolymer resin
  • a problem that it is difficult to apply to products requiring 5VA flame retardant properties.
  • studies have been conducted to further improve the 5VA flame retardant properties by additionally introducing a polyester resin, but when the polyester resin is applied, a problem in that hydrolysis resistance and the like decreases.
  • thermoplastic resin composition having excellent hydrolysis resistance, flame retardancy, impact resistance, and balance in physical properties.
  • An object of the present invention is to provide a thermoplastic resin composition excellent in hydrolysis resistance, flame retardancy, impact resistance, and balance of these properties.
  • Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.
  • thermoplastic resin composition is a rubber-modified aromatic vinyl-based copolymer resin of about 30 to about 60% by weight, polycarbonate resin of about 30 to about 60% by weight, polyester resin of about 5 to about 25% by weight of a thermoplastic resin comprising about 100% by weight part; About 0.1 to about 5 parts by weight of zinc oxide; About 0.1 to about 3 parts by weight of a phosphite compound comprising at least one of a phosphite compound represented by Formula 1 and a phosphite compound represented by Formula 2 below; And about 5 to about 30 parts by weight of a phosphorus-based flame retardant;
  • R 1 is a linear or branched alkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 5;
  • R 2 is a linear or branched alkyl group having 10 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms.
  • the rubber-modified aromatic vinyl-based copolymer resin may include a rubber-modified vinyl-based graft copolymer and an aromatic vinyl-based copolymer resin.
  • the rubber-modified vinyl-based graft copolymer may be a graft polymerization of a monomer mixture containing an aromatic vinyl-based monomer and a vinyl cyanide-based monomer in a rubbery polymer.
  • the polyester resin is polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and polytrimethylene terephthalate (PTT), polycyclohex Silene dimethylene terephthalate (PCT).
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • PTT polytrimethylene terephthalate
  • PCT polycyclohex Silene dimethylene terephthalate
  • the phosphite compound may include one or more of compounds represented by the following Formula 1a, compounds represented by the following Formula 2a, and compounds represented by the following Formula 2b.
  • the phosphorus-based flame retardant may include one or more of phosphate compounds, phosphonate compounds, phosphinate compounds, phosphine oxide compounds and phosphazene compounds.
  • thermoplastic resin composition may further include at least one of halogen-based flame retardants and antimony-based flame retardants.
  • the weight ratio of the zinc oxide and the phosphite compound may be from about 1:1 to about 4:1.
  • thermoplastic resin composition may have a flame retardancy of 5VA of a 2.5 mm thick injection specimen measured by a UL-94 vertical test method.
  • thermoplastic resin composition is exposed to a 2.5 mm thick injection specimen in a chamber at 70° C. and 95% relative humidity for 300 hours, and after aging at room temperature and 50% relative humidity for 24 hours.
  • the flame retardancy of the specimen measured by the UL-94 vertical test method may be 5VA.
  • the thermoplastic resin composition may have a notched Izod impact strength of about 20 to about 60 kgf ⁇ cm/cm of a 1/8” thick specimen measured according to ASTM D256.
  • thermoplastic resin composition may have an impact strength retention rate of about 85% or more according to Formula 1 below:
  • IZ 0 is the notched Izod impact strength of the 1/8" thick thermoplastic resin composition injection specimen measured according to ASTM D256, and IZ 1 is 300 hours in the chamber at 70°C and 95% relative humidity. It is a notched Izod impact strength measured in accordance with ASTM D256 after aging for 24 hours at 50% conditions at room temperature and relative humidity.
  • Another aspect of the invention relates to a molded article.
  • the molded article is characterized in that it is formed from the thermoplastic resin composition according to any one of 1 to 12 above.
  • the present invention has the effect of the invention to provide a thermoplastic resin composition excellent in hydrolysis resistance, flame retardancy, impact resistance, and physical properties balance, and a molded article formed therefrom.
  • thermoplastic resin composition includes (A) a rubber-modified aromatic vinyl-based copolymer resin; (B) polycarbonate resin; (C) polyester resin; (D) zinc oxide; (E) phosphite compounds; And (F) phosphorus-based flame retardants.
  • the rubber-modified aromatic vinyl-based copolymer resin according to an embodiment of the present invention may include (A1) a rubber-modified vinyl-based graft copolymer and (A2) an aromatic vinyl-based copolymer resin.
  • the rubber-modified vinyl-based graft copolymer according to an embodiment of the present invention may be a graft polymerization of a monomer mixture comprising an aromatic vinyl-based monomer and a vinyl cyanide-based monomer in a rubbery polymer.
  • the rubber-modified vinyl-based graft copolymer can be obtained by graft polymerization of a monomer mixture containing an aromatic vinyl-based monomer and a vinyl cyanide-based monomer in a rubbery polymer, and if necessary, processability and It is possible to further graft polymerize by further including a monomer that imparts heat resistance.
  • the polymerization may be performed by known polymerization methods such as emulsion polymerization and suspension polymerization.
  • the rubber-modified vinyl-based graft copolymer may form a core (rubber polymer)-shell (copolymer of a monomer mixture) structure, but is not limited thereto.
  • the rubbery polymers include diene rubbers such as polybutadiene, poly(styrene-butadiene), poly(acrylonitrile-butadiene), and saturated rubbers hydrogenated to the diene rubbers, isoprene rubber, and carbon number 2 to 2 And an alkyl (meth)acrylate rubber of 10, a copolymer of alkyl (meth)acrylate and styrene having 2 to 10 carbon atoms, an ethylene-propylene-diene monomer terpolymer (EPDM), and the like.
  • diene-based rubber, (meth)acrylate rubber, or the like can be used, and specifically, butadiene-based rubber, butyl acrylate rubber, or the like can be used.
  • the rubbery polymer (rubber particles) may have an average particle size of about 0.05 to about 6 ⁇ m, for example about 0.15 to about 4 ⁇ m, specifically about 0.25 to about 3.5 ⁇ m. In the above range, the impact resistance, appearance characteristics, and the like of the thermoplastic resin composition may be excellent.
  • the average particle size (z-average) of the rubbery polymer (rubber particles) can be measured using a light scattering method in a latex state.
  • the rubbery polymer latex is filtered through a mesh to remove coagulum generated during polymerization of the rubbery polymer, and a solution of 0.5 g of latex and 30 ml of distilled water is poured into a 1,000 ml flask and filled with distilled water to prepare a sample. , 10 ml of the sample is transferred to a quartz cell, on which the average particle size of the rubbery polymer can be measured with a light scattering particle size meter (malvern, nano-zs).
  • the content of the rubbery polymer may be about 20 to about 70% by weight, for example, about 25 to about 60% by weight, of the total of 100% by weight of the rubber-modified vinyl-based graft copolymer, and the monomer mixture (aromatic The content of the vinyl monomer and the vinyl cyanide monomer) may be about 30 to about 80% by weight, for example, about 40 to about 75% by weight, of 100% by weight of the total rubber-modified vinyl-based graft copolymer. In the above range, the impact resistance, appearance characteristics, and the like of the thermoplastic resin composition may be excellent.
  • the aromatic vinyl monomer may be graft copolymerized with the rubbery polymer, styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, And monochlorostyrene, dichlorostyrene, dibromostyrene, and vinyl naphthalene. These may be used alone or in combination of two or more.
  • the content of the aromatic vinyl-based monomer may be about 10 to about 90% by weight of 100% by weight of the monomer mixture, for example, about 40 to about 90% by weight. In the above range, the processability, impact resistance, etc. of the thermoplastic resin composition may be excellent.
  • the vinyl cyanide-based monomer is one that can be copolymerized with the aromatic vinyl-based, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, ⁇ -chloroacrylonitrile, fumaronitrile, etc. Can be illustrated. These may be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile, or the like can be used.
  • the content of the vinyl cyanide-based monomer may be about 10 to about 90% by weight of 100% by weight of the monomer mixture, for example, about 10 to about 60% by weight. In the above range, the chemical resistance and mechanical properties of the thermoplastic resin composition may be excellent.
  • (meth)acrylic acid, maleic anhydride, N-substituted maleimide, and the like may be exemplified as the monomer for imparting the processability and heat resistance, but are not limited thereto.
  • the content may be up to about 15% by weight of 100% by weight of the monomer mixture, for example, about 0.1 to about 10% by weight. Without deteriorating other physical properties in the above range, it is possible to impart processability and heat resistance to the thermoplastic resin composition.
  • the rubber-modified vinyl-based graft copolymer is a copolymer in which a styrene monomer as an aromatic vinyl-based compound and an acrylonitrile monomer as a vinyl cyanide-based compound are grafted to a butadiene-based rubber polymer (g-ABS), butadiene-based Aromatic vinyl-based styrene monomer and copolymer copolymerized with methyl methacrylate (g-MBS) as a copolymerizable monomer, and butyl acrylate-based rubber-based aromatic vinyl compound styrene monomer and vinyl cyanide
  • g-ASA acrylate-styrene-acrylonitrile graft copolymer
  • g-ASA acrylate-styrene-acrylonitrile graft copolymer
  • the rubber-modified vinyl-based graft copolymer may be included in about 20 to about 50% by weight, for example, about 25 to about 45% by weight of 100% by weight of the total rubber-modified aromatic vinyl-based copolymer resin.
  • the impact resistance of the thermoplastic resin composition, fluidity (molding processability), appearance characteristics, and balance of these properties may be excellent.
  • the aromatic vinyl-based copolymer resin according to an embodiment of the present invention may be an aromatic vinyl-based copolymer resin used in a conventional rubber-modified aromatic vinyl-based copolymer resin.
  • the aromatic vinyl-based copolymer resin may be a polymer of a monomer mixture containing an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer.
  • the aromatic vinyl-based copolymer resin can be obtained by mixing an aromatic vinyl-based monomer and an aromatic vinyl-based monomer and a copolymerizable monomer, and then polymerizing it.
  • the polymerization may be emulsion polymerization, suspension polymerization, bulk polymerization, etc. It can be carried out by a known polymerization method.
  • the aromatic vinyl monomers include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, and dibromostyrene , Vinyl naphthalene, and the like. These may be applied alone or in combination of two or more.
  • the content of the aromatic vinyl-based monomer may be about 20 to about 90% by weight, for example, about 30 to about 80% by weight, among 100% by weight of the total aromatic vinyl-based copolymer resin. In the above range, the impact resistance and fluidity of the thermoplastic resin composition may be excellent.
  • the monomer copolymerizable with the aromatic vinyl monomer may include at least one of a vinyl cyanide monomer and an alkyl (meth)acrylic monomer.
  • a vinyl cyanide monomer and an alkyl (meth)acrylic monomer may be a vinyl cyanide monomer or a vinyl cyanide monomer and an alkyl (meth)acrylic monomer, specifically, a vinyl cyanide monomer and an alkyl (meth)acrylic monomer.
  • the vinyl cyanide-based monomer may be exemplified by acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, ⁇ -chloroacrylonitrile, fumaronitrile, etc., but is not limited thereto. Does not. These may be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile, or the like can be used.
  • the alkyl (meth)acrylic monomer may include (meth)acrylic acid and/or alkyl (meth)acrylate having 1 to 10 carbon atoms. These may be used alone or in combination of two or more. For example, methyl methacrylate, methyl acrylate, and the like can be used.
  • the content of the vinyl cyanide monomer is 100% by weight of the monomer copolymerizable with the aromatic vinyl monomer. It may be 1 to 40% by weight, for example, 2 to 35% by weight, and the content of the alkyl (meth)acrylic monomer is about 60 to about 99% by weight of 100% by weight of the monomer copolymerizable with the aromatic vinyl monomer, For example, about 65 to about 98% by weight. In the above range, the transparency, heat resistance, and workability of the thermoplastic resin composition may be excellent.
  • the content of the aromatic vinyl-based monomer and the copolymerizable monomer may be about 10 to about 80% by weight, for example, about 20 to about 70% by weight, among 100% by weight of the aromatic vinyl-based copolymer resin. In the above range, the impact resistance and fluidity of the thermoplastic resin composition may be excellent.
  • the aromatic vinyl-based copolymer resin has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 10,000 to about 300,000 g/mol, for example, about 15,000 to about 150,000 g/mol. Can.
  • Mw weight average molecular weight measured by gel permeation chromatography
  • GPC gel permeation chromatography
  • the aromatic vinyl-based copolymer resin may be included in about 50 to about 80% by weight, for example, about 55 to about 75% by weight of 100% by weight of the total rubber-modified aromatic vinyl-based copolymer resin.
  • the impact resistance of the thermoplastic resin composition, fluidity (molding processability), and the like may be excellent.
  • the rubber-modified aromatic vinyl-based copolymer resin (A) is 100% by weight of a thermoplastic resin (rubber-modified aromatic vinyl-based copolymer resin (A), polycarbonate resin (B) and polyester resin (C)) , About 30 to about 60% by weight, for example about 35 to about 55% by weight, specifically about 40 to about 50% by weight.
  • a thermoplastic resin rubber-modified aromatic vinyl-based copolymer resin (A), polycarbonate resin (B) and polyester resin (C)
  • about 30 to about 60% by weight for example about 35 to about 55% by weight, specifically about 40 to about 50% by weight.
  • the content of the rubber-modified aromatic vinyl-based copolymer resin is less than about 30% by weight, the impact resistance and hydrolysis resistance of the thermoplastic resin composition may be deteriorated, and when it exceeds about 60% by weight, flame retardancy, fluidity, etc. There is a fear that this may decrease.
  • a polycarbonate resin used in a conventional thermoplastic resin composition may be used.
  • an aromatic polycarbonate resin produced by reacting diphenols (aromatic diol compounds) with precursors such as phosgene, halogen formate, and carbonic acid diester can be used.
  • the diphenols include 4,4'-biphenol, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1 ,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl) Propane and the like, but is not limited thereto.
  • 2,2-bis(4-hydroxyphenyl)propane 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, or 1,1-bis(4-hydroxyphenyl) )Cyclohexane
  • 2,2-bis(4-hydroxyphenyl)propane called bisphenol-A can be used.
  • the polycarbonate resin may be used having a branched chain, for example, about 0.05 to about 2 mol% of trivalent or higher polyfunctional compound, specifically with respect to the total diphenols used for polymerization, specifically , It is also possible to use a branched polycarbonate resin prepared by adding a compound having a trivalent or higher phenol group.
  • the polycarbonate resin may be used in the form of a homo polycarbonate resin, a copolycarbonate resin, or a blend thereof.
  • the polycarbonate resin may be partially or wholly substituted with an aromatic polyester-carbonate resin obtained by polymerization reaction in the presence of an ester precursor, such as a bifunctional carboxylic acid.
  • the polycarbonate resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 10,000 to about 50,000 g/mol, for example, about 15,000 to about 40,000 g/mol.
  • Mw weight average molecular weight measured by gel permeation chromatography
  • the flowability (processability) of the thermoplastic resin composition in the above range may be excellent.
  • the polycarbonate resin (B) is a thermoplastic resin (rubber-modified aromatic vinyl-based copolymer resin (A), polycarbonate resin (B) and polyester resin (C)) of 100% by weight, about 30 to about 60% by weight, for example about 30 to about 50% by weight, specifically about 35 to about 45% by weight.
  • thermoplastic resin rubber-modified aromatic vinyl-based copolymer resin (A), polycarbonate resin (B) and polyester resin (C)
  • the content of the polycarbonate resin is less than about 30% by weight, the flame retardancy and impact resistance of the thermoplastic resin composition may be lowered, and when it exceeds about 60% by weight, there is a fear that fluidity and hydrolysis resistance are lowered. have.
  • the polyester resin is a dicarboxylic acid component, terephthalic acid (TPA), isophthalic acid (IPA), 1,2-naphthalene dicarboxylic acid, 1,4-naphthalene dicar Carboxylic acid, 1,5-naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid Aromatic dicarboxylic acids such as carboxylic acid, 2,6-naphthalene dicarboxylic acid and 2,7-naphthalenedicarboxylic acid, dimethyl terephthalate (DMT), dimethyl isophthalate, dimethyl- 1,2-naphthalate, dimethyl-1,5-naphthalate, dimethyl-1,
  • DMT dimethyl terephthalate
  • the polyester resin is polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and polytrimethylene terephthalate (PTT), polycyclohexylenedimethylene terephthalate ( PCT).
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • PTT polytrimethylene terephthalate
  • PCT polycyclohexylenedimethylene terephthalate
  • the polyester resin of the present invention has an intrinsic viscosity [ ⁇ ] measured using an o-chlorophenol solvent at 25° C. of about 0.5 to about 1.5 dl/g, for example, about 0.6 to about 1.3 dl/ It can be g. In the above range, flame retardancy, mechanical properties, and the like of the thermoplastic resin composition may be excellent.
  • the polyester resin (C) is a thermoplastic resin (rubber-modified aromatic vinyl-based copolymer resin (A), polycarbonate resin (B) and polyester resin (C)) in 100% by weight, about 5 to about 25% by weight, for example about 7 to about 22% by weight, specifically about 10 to about 20% by weight.
  • the content of the polyester resin is less than about 5% by weight, the flame retardancy, fluidity (processability), etc. of the thermoplastic resin composition may be lowered, and when it exceeds about 25% by weight, impact resistance, hydrolysis resistance, etc. are lowered. It might be.
  • the zinc oxide of the present invention can be applied together with a specific phosphite compound to improve the hydrolysis resistance, impact resistance, flame retardancy, and balance of physical properties of the thermoplastic resin composition, and zinc oxide used in a common thermoplastic resin composition Can be used.
  • the zinc oxide is an average particle size (D50) of a single particle (particles do not aggregate to form secondary particles) measured using a particle size analyzer (Beckman Coulter's Laser Diffraction Particle Size Analyzer LS I3 320 equipment) Can be about 0.2 to about 3 ⁇ m, for example about 0.5 to about 3 ⁇ m.
  • the zinc oxide using a nitrogen gas adsorption method is about 1 to about 10 m 2 /g, for example, about 1 To about 7 m 2 /g, and the purity may be 99% or more. In the above range, the discoloration resistance, antibacterial property, etc. of the thermoplastic resin composition may be excellent.
  • the zinc oxide may have various forms, and may include, for example, spherical, plate, rod, and combinations thereof.
  • the zinc oxide (D) is about 0.1 to about 100 parts by weight of the thermoplastic resin (rubber-modified aromatic vinyl-based copolymer resin (A), polycarbonate resin (B) and polyester resin (C)) To about 5 parts by weight, for example about 0.2 to about 4 parts by weight, specifically about 0.5 to about 2 parts by weight.
  • the content of the zinc oxide is less than about 0.1 parts by weight with respect to about 100 parts by weight of the thermoplastic resin, there is a possibility that the hydrolysis resistance and impact resistance of the thermoplastic resin composition are lowered, and when it exceeds about 5 parts by weight, the thermoplastic There is a fear that the impact resistance, flame retardancy, and hydrolysis resistance of the resin composition are lowered.
  • Phosphite (phosphite) compound of the present invention is applied together with zinc oxide, to improve the hydrolysis resistance, impact resistance, flame retardancy, balance of these properties, etc. of the thermoplastic resin composition, phosphite represented by the following formula (1)
  • Compounds and/or phosphite compounds represented by the following formula (2) can be used.
  • R 1 is a linear or branched alkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 5, for example, an integer of 2 to 4.
  • R 1 may be at least one branched alkyl group, for example, tert-butyl group.
  • R 2 is a linear or branched alkyl group having 10 to 30 carbon atoms, for example, a linear alkyl group having 15 to 25 carbon atoms, or an aryl group having 6 to 30 carbon atoms, for example, a linear group having 1 to 4 carbon atoms, or It is a phenyl group substituted with a branched alkyl group.
  • the phosphite compound may include at least one of a compound represented by Formula 1a, a compound represented by Formula 2a, and a compound represented by Formula 2b.
  • the phosphite compound (E) is about 100 parts by weight of the thermoplastic resin (rubber-modified aromatic vinyl-based copolymer resin (A), polycarbonate resin (B) and polyester resin (C)), about 0.1 to about 3 parts by weight, for example, about 0.1 to about 2 parts by weight, specifically about 0.2 to about 1.5 parts by weight.
  • the content of the phosphorus-based flame retardant is less than about 0.1 parts by weight with respect to about 100 parts by weight of the thermoplastic resin, there is a possibility that the hydrolysis resistance and impact resistance of the thermoplastic resin composition decrease, and when it exceeds about 3 parts by weight, thermoplastic There is a possibility that the hydrolysis resistance and impact resistance of the resin composition are lowered.
  • the weight ratio (D:E) of the zinc oxide (D) and the phosphite compound (E) may be about 1: 1 to about 10: 1, for example, about 1: 1 to about 4: 1 have.
  • the hydrolysis resistance, impact resistance, flame retardancy, and balance of physical properties of the thermoplastic resin composition may be more excellent.
  • Phosphorus-based flame retardant according to an embodiment of the present invention may be a phosphorus-based flame retardant used in a conventional thermoplastic resin composition.
  • phosphorus-based flame retardants such as phosphate compounds, phosphonate compounds, phosphinate compounds, phosphine oxide compounds, phosphazene compounds, and metal salts thereof Can be used. These may be used alone or in combination of two or more.
  • the phosphorus-based flame retardant may include an aromatic phosphate ester compound (phosphate compound) represented by the following Chemical Formula 3.
  • phosphate compound represented by the following Chemical Formula 3.
  • R 1 , R 2 , R 4 and R 5 are each independently a hydrogen atom, a C6-C20 aryl group having 6 to 20 carbon atoms, or a C6-C20 aryl substituted with a C1-C10 alkyl group.
  • Group, and R 3 is a C6-C20 arylene group or a C1-C10 alkyl group substituted C6-C20 arylene group, for example, dialcohols such as resorcinol, hydroquinone, bisphenol-A, bisphenol-S, etc.
  • n is an integer from 0 to 10, for example 0 to 4.
  • bisphenol-A diphosphate bisphenol-A bis(diphenylphosphate), resorcinol bis(diphenylphosphate), resorcinol bis[bis(2,6-dimethylphenyl)phosphate], resorcinol bis [Bis(2,4-diterybutylphenyl)phosphate], hydroquinone bis[bis(2,6-dimethylphenyl)phosphate], hydroquinone bis[bis(2,
  • the phosphorus-based flame retardant (F) is about 5 parts by weight based on about 100 parts by weight of the thermoplastic resin (rubber-modified aromatic vinyl-based copolymer resin (A), polycarbonate resin (B), and polyester resin (C)) To about 30 parts by weight, for example, about 7 to about 20 parts by weight, specifically about 9 to about 18 parts by weight.
  • the content of the phosphorus-based flame retardant is less than about 5 parts by weight with respect to about 100 parts by weight of the thermoplastic resin, there is a fear that the flame retardancy, fluidity, etc. of the thermoplastic resin composition are lowered, and when it exceeds about 30 parts by weight, the thermoplastic resin composition There is a fear that impact resistance and the like are deteriorated.
  • thermoplastic resin composition according to an embodiment of the present invention may further include a flame retardant other than a phosphorus-based flame retardant, such as a halogen-based flame retardant, an antimony-based flame retardant, and combinations thereof, to further improve flame retardancy.
  • a flame retardant other than a phosphorus-based flame retardant such as a halogen-based flame retardant, an antimony-based flame retardant, and combinations thereof, to further improve flame retardancy.
  • the halogen-based flame retardant is decabromodiphenyl oxide, decabromodiphenylethane, decabromodiphenyl ether, tetrabromobisphenol A, tetrabromobisphenol A-epoxy oligomer, brominated epoxy oligomer, octave Lomotrimethylphenylindan, ethylenebistetrabromophthalimide, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, etc.
  • the antimony-based flame retardant include antimony trioxide, antimony pentoxide, and the like. These may be used alone or in combination of two or more.
  • the flame retardant excluding the phosphorus-based flame retardant is about 5 parts by weight based on about 100 parts by weight of the thermoplastic resin (rubber-modified aromatic vinyl-based copolymer resin (A), polycarbonate resin (B), and polyester resin (C)) To about 20 parts by weight, for example, about 7 to about 10 parts by weight. In the above range, the flame retardancy and the like of the thermoplastic resin composition may be excellent.
  • the thermoplastic resin composition according to an embodiment of the present invention may further include an additive included in a conventional thermoplastic resin composition.
  • the additives include, but are not limited to, dripping inhibitors such as fluorinated olefin resins, lubricants, nucleating agents, stabilizers, mold release agents, pigments, dyes, and mixtures thereof.
  • the content may be about 0.001 to about 40 parts by weight, for example, about 0.1 to about 10 parts by weight with respect to about 100 parts by weight of the thermoplastic resin.
  • thermoplastic resin composition according to an embodiment of the present invention is a pellet form in which the above components are mixed and melt-extruded at about 200 to about 280°C, for example, from about 220 to about 250°C, using a conventional twin-screw extruder. Can.
  • thermoplastic resin composition may have a flame retardancy of 5VA of a 2.5 mm thick injection specimen measured by UL-94 vertical test method.
  • thermoplastic resin composition is exposed to a 2.5 mm thick injection specimen in a chamber at 70° C. and 95% relative humidity for 300 hours, and after aging at room temperature and 50% relative humidity for 24 hours, UL-94 vertical test Flame retardancy of the specimen measured by the method may be 5VA.
  • the thermoplastic resin composition has a notch Izod impact strength of 1/8" thick specimens measured according to ASTM D256, about 20 to about 60 kgfcm/cm, for example about 30 to about 50 kgf. It may be cm / cm.
  • thermoplastic resin composition may have an impact strength retention of about 85% or more according to the following Equation 1, for example, about 90 to about 99%.
  • IZ 0 is the notched Izod impact strength of the 1/8" thick thermoplastic resin composition injection specimen measured according to ASTM D256, and IZ 1 is 300 hours in the chamber at 70°C and 95% relative humidity. It is a notched Izod impact strength measured in accordance with ASTM D256 after aging for 24 hours at 50% conditions at room temperature and relative humidity.
  • the molded article according to the present invention is formed from the thermoplastic resin composition.
  • the thermoplastic resin composition may be manufactured in a pellet form, and the manufactured pellet may be manufactured into various molded products (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known by those skilled in the art to which this invention pertains.
  • the molded article is excellent in hydrolysis resistance, flame retardancy, impact resistance, and balance of these properties, and is useful as interior/exterior materials for electric/electronic products, interior/exterior materials for automobiles, exterior materials for construction, and the like.
  • Graft in core-shell form prepared by graft copolymerization of styrene and acrylonitrile (styrene/acrylonitrile: 75 wt%/ 25 wt%) to 58 wt% butadiene rubber having an average particle size of 0.3 ⁇ m Copolymer (g-ABS) was used.
  • a bisphenol-A type polycarbonate resin having a weight average molecular weight (Mw) of 22,000 g/mol was used.
  • PET Polyethylene terephthalate
  • Notched Izod impact strength (unit: kgfcm/cm): Notched Izod impact strength of a 1/8" thick specimen was measured according to ASTM D256.
  • IZ 0 is the notched Izod impact strength of the 1/8" thick thermoplastic resin composition injection specimen measured according to ASTM D256, and IZ 1 is 300 hours in the chamber at 70°C and 95% relative humidity. It is a notched Izod impact strength measured in accordance with ASTM D256 after aging for 24 hours at 50% conditions at room temperature and relative humidity.
  • thermoplastic resin composition of the present invention is excellent in hydrolysis resistance (flame retardancy after high temperature/high humidity treatment, impact strength retention rate), flame retardancy, impact resistance, and balance of physical properties thereof.
  • Comparative Example 1 in which a small amount of the rubber-modified aromatic vinyl-based copolymer resin was applied and the polyester resin was excessively applied, it was found that impact resistance, hydrolysis resistance (impact strength retention), and the like were lowered, and rubber-modified aromatic vinyl.
  • Comparative Example 2 in which an excess amount of the copolymer resin was applied and a small amount of the polyester resin was applied, it was found that flame retardancy, hydrolysis resistance (retardance after high temperature/high humidity treatment), and the like were lowered.
  • Comparative Example 3 without zinc oxide and Comparative Example 4 with small amount applied, it was found that the impact resistance and hydrolysis resistance (retardance and impact strength retention rate after high/high temperature treatment) were deteriorated, and zinc oxide was applied in excess.
  • Comparative Example 5 it can be seen that flame retardancy, hydrolysis resistance (flame retardancy after high temperature/high humidity treatment), etc.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Une composition de résine thermoplastique selon la présente invention comprend : environ 100 parties en poids d'une résine thermoplastique comprenant environ 30 à environ 60 % en poids d'une résine copolymère à base de vinyle aromatique modifiée par du caoutchouc, environ 30 à environ 60 % en poids d'une résine de polycarbonate, et environ 5 à environ 25 % en poids d'une résine de polyester ; environ 0,1 à environ 5 parties en poids d'oxyde de zinc ; environ 0,1 à environ 3 parties en poids d'un composé de phosphite comprenant au moins un type choisi parmi un composé de phosphite représenté par la formule chimique 1 et un composé de phosphite représenté par la formule chimique 2 ; et environ 5 à environ 30 parties en poids d'un agent ignifuge à base de phosphore. La composition de résine thermoplastique présente une excellente résistance à l'hydrolyse, un excellent caractère ignifuge, une excellente résistance aux chocs, un excellent équilibre de ces propriétés physiques, et analogues.
PCT/KR2019/017783 2018-12-28 2019-12-16 Composition de résine thermoplastique et article moulé produit à partir de celle-ci WO2020138802A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US17/284,858 US20210388140A1 (en) 2018-12-28 2019-12-16 Thermoplastic Resin Composition and Molded Article Therefrom
EP19901687.4A EP3904455A4 (fr) 2018-12-28 2019-12-16 Composition de résine thermoplastique et article moulé produit à partir de celle-ci
CN201980075671.5A CN113056521A (zh) 2018-12-28 2019-12-16 热塑性树脂组合物和来自其的模制品

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2018-0172708 2018-12-28
KR1020180172708A KR102183731B1 (ko) 2018-12-28 2018-12-28 열가소성 수지 조성물 및 이로부터 형성된 성형품

Publications (1)

Publication Number Publication Date
WO2020138802A1 true WO2020138802A1 (fr) 2020-07-02

Family

ID=71126590

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2019/017783 WO2020138802A1 (fr) 2018-12-28 2019-12-16 Composition de résine thermoplastique et article moulé produit à partir de celle-ci

Country Status (5)

Country Link
US (1) US20210388140A1 (fr)
EP (1) EP3904455A4 (fr)
KR (1) KR102183731B1 (fr)
CN (1) CN113056521A (fr)
WO (1) WO2020138802A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102559676B1 (ko) * 2020-08-31 2023-07-25 롯데케미칼 주식회사 열가소성 수지 조성물 및 이로부터 형성된 성형품
KR102639840B1 (ko) * 2021-08-30 2024-02-22 롯데케미칼 주식회사 열가소성 수지 조성물 및 이로부터 제조된 성형품

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR245E (fr) 1901-05-18 1902-11-24 Dupont Système perfectionné de chauffe-bain
US5061745A (en) 1988-06-04 1991-10-29 Bayer Aktiengesellschaft Flame-retardant, high-impact polycarbonate molding compounds
JPH0841305A (ja) * 1994-04-07 1996-02-13 General Electric Co <Ge> 高割合の充填剤を含有し、斑点状表面外観をもつ押出熱可塑性樹脂組成物
US20040249030A1 (en) * 2003-06-05 2004-12-09 Enlow William Palmer Polymer compositions containing stabilizer compounds comprising tricyclodecylmethyl groups
KR20070047073A (ko) * 2005-11-01 2007-05-04 주식회사 엘지화학 열안정성, 내광변색성 및 내후성이 우수한 열가소성 수지조성물
KR20080032487A (ko) * 2006-10-10 2008-04-15 주식회사 엘지화학 열가소성 난연수지 조성물
US20150322252A1 (en) * 2012-12-20 2015-11-12 Polyad Services Llc Flame retardant polymer compositions
KR20160079786A (ko) * 2013-11-01 2016-07-06 사빅 글로벌 테크놀러지스 비.브이. 보강된 난연제 폴리카보네이트 조성물 및 이를 포함하는 성형 물품

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100379658B1 (ko) * 2000-12-27 2003-04-11 제일모직주식회사 광안정성이 우수한 열가소성 난연성 수지 조성물
KR101664845B1 (ko) * 2013-06-28 2016-10-11 롯데첨단소재(주) 저수축 열가소성 수지 조성물 및 이를 포함하는 성형품

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR245E (fr) 1901-05-18 1902-11-24 Dupont Système perfectionné de chauffe-bain
US5061745A (en) 1988-06-04 1991-10-29 Bayer Aktiengesellschaft Flame-retardant, high-impact polycarbonate molding compounds
JPH0841305A (ja) * 1994-04-07 1996-02-13 General Electric Co <Ge> 高割合の充填剤を含有し、斑点状表面外観をもつ押出熱可塑性樹脂組成物
US20040249030A1 (en) * 2003-06-05 2004-12-09 Enlow William Palmer Polymer compositions containing stabilizer compounds comprising tricyclodecylmethyl groups
KR20070047073A (ko) * 2005-11-01 2007-05-04 주식회사 엘지화학 열안정성, 내광변색성 및 내후성이 우수한 열가소성 수지조성물
KR20080032487A (ko) * 2006-10-10 2008-04-15 주식회사 엘지화학 열가소성 난연수지 조성물
US20150322252A1 (en) * 2012-12-20 2015-11-12 Polyad Services Llc Flame retardant polymer compositions
KR20160079786A (ko) * 2013-11-01 2016-07-06 사빅 글로벌 테크놀러지스 비.브이. 보강된 난연제 폴리카보네이트 조성물 및 이를 포함하는 성형 물품

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3904455A4

Also Published As

Publication number Publication date
EP3904455A4 (fr) 2022-08-31
EP3904455A1 (fr) 2021-11-03
KR20200082276A (ko) 2020-07-08
CN113056521A (zh) 2021-06-29
KR102183731B1 (ko) 2020-11-27
US20210388140A1 (en) 2021-12-16

Similar Documents

Publication Publication Date Title
WO2011081287A2 (fr) Composition de résine thermoplastique comprenant un composé de phosphore polymérisé, une pièce moulée en plastique fabriquée de la composition, et procédé pour fabriquer un composé de phosphore polymérisé
WO2014092412A1 (fr) Composition de résine polycarbonate ayant une excellente résistance à la lumière et un excellent retard de feu et produit moulé la comprenant
WO2011013882A1 (fr) Composition de résine thermoplastique et articles moulés comprenant cette dernière
WO2012015109A1 (fr) Composition de résine de polycarbonate ignifuge présentant d&#39;excellentes résistance aux rayures et résistance aux chocs et produit moulé à base de ladite résine
WO2012060515A1 (fr) Composition de résine de polycarbonate retardatrice de flamme et résistante aux rayures
WO2020138802A1 (fr) Composition de résine thermoplastique et article moulé produit à partir de celle-ci
WO2019132584A1 (fr) Composition de résine thermoplastique et produit moulé formé à partir de celle-ci
WO2021020741A1 (fr) Composition de résine thermoplastique et article moulé formé à partir de celle-ci
WO2019066193A1 (fr) Composition de résine thermoplastique résistante aux rayonnements ionisants et article moulé comprenant celle-ci
WO2019132575A1 (fr) Composition de résine thermoplastique et article moulé fabriqué à partir de celle-ci
TW201842056A (zh) 熱塑性聚酯樹脂組成物及成形品
WO2018124790A2 (fr) Composition de résine de polyoléfine et article moulé l&#39;utilisant
WO2010067926A1 (fr) Nouveaux composés de phosphate, leur procédé de préparation, et compositions de résine thermoplastique ignifuges utilisant de tels composés
WO2013100303A1 (fr) Composition de résine à base de polycarbonate à haute brillance et article moulé à partir de celle-ci
WO2020138785A1 (fr) Composition de résine thermoplastique et produit moulé formé à partir de celle-ci
WO2020111618A1 (fr) Composition de résine thermoplastique et article produit à partir de celle-ci
WO2013042827A1 (fr) Polycarbonate et son procédé de production
WO2018117438A1 (fr) Composition de résine et produit moulé fabriqué à partir de cette composition de résine
WO2015064859A1 (fr) Composition de résine thermoplastique ayant une excellente résistance chimique et dureté selon b.o.s.s.
WO2019132572A1 (fr) Composition de résine thermoplastique et article moulé fabriqué avec celle-ci
WO2021085867A1 (fr) Composition de résine thermoplastique et produit moulé fabriqué à partir de celle-ci
WO2013100295A1 (fr) Composition de résine thermoplastique ignifuge et produit moulé fabriqué à partir de celle-ci
WO2020004830A1 (fr) Composition de résine thermoplastique et produit moulé fabriqué à partir de celle-ci
WO2019139386A1 (fr) Composition de résine thermoplastique
WO2019212222A1 (fr) Composition de résine thermoplastique et article moulé comprenant celle-ci

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19901687

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2019901687

Country of ref document: EP

Effective date: 20210728